Highly Axial Magnetic Anisotropy in a N3O5 Dysprosium(III) Coordination Environment Generated by a Merocyanine Ligand

A spiropyran‐based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N₃O₅ coordination sphere. The air‐stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor.     

Kinematics in matrix gravity

We develop the kinematics in Matrix Gravity, which is a modified theory of gravity obtained by a non-commutative deformation of General Relativity. In this model the usual interpretation of gravity as Riemannian geometry is replaced by a new kind of geometry, which is equivalent to a collection of Finsler geometries with several Finsler metrics depending both on the position and on the velocity. As a result the Riemannian geodesic flow is replaced by a collection of Finsler flows. This naturally leads to a model in which a particle is described by several mass parameters. If these mass parameters are different then the equivalence principle is violated. In the non-relativistic limit this also leads to corrections to the Newton’s gravitational potential. We find the first and second order corrections to the usual Riemannian geodesic flow and evaluate the anomalous nongeodesic acceleration in a particular case of static spherically symmetric background.     

A mathematical program to refine gene regulatory networks

In this paper, we propose a methodology for making sense of large, multiple time-series data sets arising in expression analysis. Specifically, we present a mathematical model to release a reduced and coherent regulatory system given a putative regulatory network. We give two equivalent formulations of the problem and prove that the problem is NP-complete. For solving large scale instances we implemented an Ant Colony Optimization procedure. A computational analysis on randomly generated test instances validates the proposed algorithm and the computations on real data concerning Saccharomyces cerevisiae show the practicability of the proposed methodology.     

A semi-Markov maintenance model with credit rating application

Email: g.damico{at}unich.it Received on 6 December 2006. Accepted on 2 April 2008. The impact of a preventive rating maintenance policy on therating process is investigated through the definition of a semi-Markovmaintenance model with imperfect repair at random times. Theresults allow us to study the rating migrations process in thetransient and the asymptotic case.     

Band-edge ultrafast pump-probe spectroscopy of core/shell CdSe/CdS rods: assessing electron delocalization by effective mass calculations

CdSe/CdS dot/rods nanocrystals show interesting physical properties related to the band-alignment at the hetero-interface, which controls the band-edge electron delocalization over the rods. Here the differential transmission spectra of CdSe/CdS nanorod samples with different core sizes have been measured using excitation resonant to the core transition. The photo bleaching ratio between dot and rod transitions increases with the dot size, indicating a trend towards electron localization. This trend has been further quantified by performing effective mass calculations in which the conduction band misalignment was varied in order to reproduce the observed bleaching feature ratio. The best agreement was found for negligible conduction band misalignment for small dots of around 2.3 nm in diameter, and about -0.1 eV misalignment was estimated for the larger dots, above 3.5 nm in diameter. This shows that the band misalignment might be dependent on the geometry of the system, and we argue that this might be related to different strain developed at the hetero-interface.     

Cavitand-functionalized porous silicon as an active surface for organophosphorus vapor detection

This paper reports on the preparation of a porous silicon-based material covalently functionalized with cavitand receptors suited for the detection of organophosphorus vapors. Two different isomeric cavitands, both containing one acid group at the upper rim, specifically designed for covalent anchoring on silicon, were grafted on H-terminated porous silicon (PSi) by thermal hydrosilylation. The covalently functionalized surfaces and their complexation properties were characterized by combining different analytical techniques, namely X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and mass spectroscopy analysis coupled with thermal desorption experiments. Complexation experiments were performed by exposing both active surfaces and a control surface consisting of PSi functionalized with a structurally similar but inactive methylene-bridged cavitand (MeCav) to dimethyl methylphosphonate (DMMP) vapors. Comparison between active and inactive surfaces demonstrated the recognition properties of the new surfaces. Finally, the nature of the involved interactions, the energetic differences between active and inactive surfaces toward DMMP complexation, and the comparison with a true nerve gas agent (sarin) were studied by DFT modeling. The results revealed the successful grafting reaction, the specific host-guest interactions of the PSi-bonded receptors, and the reversibility of the guest complexation.     

Modeling triplet flavin-indole electron transfer and interradical dipolar interaction: a perturbative approach

A benchmark biochemical reaction is here theoretically investigated by means of a perturbative approach in order to model each reaction step. The reaction is the flavin-indole electron transfer, involving also a spin-state relaxation of the ionic complex. The whole reaction path is modeled and the kinetics of the process is studied. The dipolar interaction between the two radicals is explicitly considered during the dynamic evolution of the system in order to investigate the proper conditions for the triplet-to-singlet transition to occur.     

Spectral and kinetic evidence for attack at coordinated phenanthroline in the reaction between aliphatic amines and transition metal complexes of 5-nitro-1,10-phenanthroline

Various transition metal complexes of 5-nitro-1,10-phenanthroline react with aliphatic amines in dipolar aprotic solvents to give deeply coloured species. The spectral changes, which can be reversed upon addition of acid or of the appropriate protonated amine, do not depend either on the nature of the metal and the ancillary ligands or on the geometry of the complexes; this has been taken as evidence that the colour forming process is due to a specific interaction of aliphatic amines with coordinated phenanthroline. While the rate of reaction of [Pt(5-NO₂phen)Cl₂] and [Pd(5-NO₂phen)Cl₂] with Br^?, which is known to displace Cl^? in the substrates, depends strongly on the nature of the central atom, the second order rate constant at 25°C being 3.2 × 10^?4 dm³mol^?1s^?1 and 1.35 dm³mol^?1s^?1 for the platinum and the palladium derivative respectively, the rate of reaction with n-propylamine has a comparable value for both substrates. This is further evidence that amines attack the coordinated phenanthroline, rather than the central atom. On the basis of the spectral features and the reaction stoicheiometry, the adducts of metal complexes of 5-NO₂phen and aliphatic amines are presumably Meisenheimer-like complexes.     

Possible Tests of Curvature Effects in Weak Gravitational Fields

The possibility of performing in proximity of the Earth experiments to test the predictions of general relativity for the trajectories of particles and photons in weak gravitational fields is studied. Three experiments are analyzed, all based on optical detection methods. The first experiment would allow to detect the tidal acceleration using a freely-falling Michelson interferometer. In a second experiment, based on laser-ranging methods, the relativistic correction to the classical gravity acceleration could be detected. Finally, the possibility of detecting light deflection induced by space curvature in an optical cavity with high-reflectivity mirrors is discussed.